Process for oxidizing soluble alkylene bisdithiocarbamates to produce an oxygen containing product, and the product of said process



Sept. 10, 1968 A. M. HARVEY ETAL 3,403,12

PROCESS FOR OXIDIZING SOLUBLE ALKYLENE BISDITHIOCARBAMATES TO PRODUCE AN OXYGEN CONTAINING PRODUCT, AND THE PRODUCT OF SAID PROCESS Filed May 15, 1964 5 Sheets-Sheet 1 7 a 9 man wAvaEmm (MICRONS) mscusucv (cw) ZINC SALT ABSORBANCE 7 8 9 BBQ WAVELBIGTH (MICRONS) Fl G. 2

INVENTORS ALLAN M. HARVEY LESTER A. BROOKS Sept. 10, 1968 A. M. HARVEY ETAL. 3,401,132

PROCESS FOR OXIDIZING SOLUBLE ALKYLENE BISDITHIOCARBAMATES TO PRODUCE AN OXYGEN CONTAINING PRODUCT, AND THE PRODUCT OF SAID PROCESS Filed May 15, 1964 5 Sheets-Sheet 2 FREQUENCY (CM) 7 s 9 I353 WAVELENGYH (muons) FREQUENCY (CM) 7 a 9 E g WAVELENGTH (muons) FIG. 4

INVENTORS ALLAN M. HARVEY LESTER A. BROOKS Sept. 10, 1968 A. M. HARVEY ETAL. 3,401,182

PROCESS FOR OXIDIZING SOLUBLE ALKYLENE] BISDITHIOCARBAMATES TO PRODUCE AN OXYGEN CONTAINING PRODUCT, AND THE PRODUCT OF SAID PROCESS 5 Sheets-Sheet 5 Filed May 15, 1964 FREQUENCY (CM) 10000 50004000 3000 2500 ZXXJIBW NABAM WAVELBQGTH (MICRON) FREQUENCY (cw) WAVELENGTH (MICRONS) INVENTORS ALLAN M. HARVEY LESTER A. BROOKS ABSORBANCE Sept. 10,1968 A. M. HARVEY ETAL 3,401,182

PROCESS FOR OXIDIZING SOLUBLE ALKYLENE BISDITHIOCARBAMATES To PRODUCE AN OXYGEN CONTAINING PRODUCT, AND THE PRODUCT OF SAID PROCESS Filed May 15, 1964 s Sheets-Sheet 4 FREQUENCY (CJW) I 2 a 4 5 6 7 a 9 [in] WAVELENGTH (MICRONS) \0 I] I2 13 H 15 V 7 8 9 (BBQ WAVELENGTH (mozous) INVENTORS ALLAN M. HARVEY LESTER A. BROOKS P 1968 A. M. HARVEY ETAL 3, 82

PROCESS FOR OXIDIZING SOLUBLE ALKYLENE BISDITHIOCARBAMATES TO PRODUCE AN OXYGEN CONTAINING PRODUCT, AND THE PRODUCT OF SAID PROCESS Filed May 15, 1964 5 Sheets-Sheet 5 FREQUBKY (CW) ABSORBAME 7 e 9 353 wAvaENcm (muons) FIG.9

INVEN TORS ALLAN M. HARVEY LESTER A. BROOKS wol gm United States atet Norwalk, Conm, assignors to R. T. Vanderbilt Com-.

pany, Inc, New York, N.Y., a corporation of New York Filed May 15, 1964, Ser. No. 367,620 20 Claims. (Cl. 260-429) ABSTRACT OF THE DISCLOSURE The disclosure of the application is directed to a process for oxidizing certain soluble alkylene bisdithiocarbamates using hydrogen peroxide as the oxidizing agent without .adding acid in an amount to convert all of the bisdithiocarbamate to the corresponding bisdithiocarbamic acid, under conditions to produce a soluble oxygen containing product. Such soluble oxygen containing product is thereafter treated with .a solution of soluble salt of a divalent metal of zinc, manganese, copper or cadmium, thereby to precipitate a product containing oxygen and such divalent metal. The infrared absorption spectra of such products, and the method for combating fungus on growing agricultural crops, such as potato plants, are also described.

where X is the metal zinc or divalent manganese. Similar compounds of other metals are also known. These compounds can be prepared by treating the sodium salt of ethylene bisdithiocarbamic acid (nabam) in aqueous solution with a soluble zinc or manganous salt such as zinc or manganous sulfate and recovering the precipitated product that forms.

The prior art also discloses the manufacture of metal free oxidized products of soluble ethylene bisdithiocarbamates, the ethylene bisthiurarn monosulfide and ethylene bisthiuram disulfide having the following formulas:

The latter compounds are prepared from ammonium or soluble metal ethylene bisdithiocarbamates by treating them with any of a variety of oxidizing agents and under a variety of conditions to produce the indicated compounds or mixtures of thiuram monoand disulfides along with free sulfur and sometimes ethylenethiourea. Under acid conditions nabam oxidized with air in the presence of the manganous ion as catalyst, or the am- 3,4lll,l82 Patented Sept. 10, 1968 monium salt oxidized with hydrogen peroxide at a pH of 6.5, yields ethylene bisthiuram disulfide.- Under neutral conditions it yields polymeric ethylene bisthiuram monosulfide and under alkaline conditions, the monomeric ethylene bisthiuram monosulfide is obtained.

It has now been discovered that the oxidation of soluble ethylene bisdithiocarbamate" under certain prescribed conditions, hereinafter more fullyset forth, results in the formation of a-new oxygen-containing material which forms divalent metal salts. Such materialshave also been found to possess very desirable properties.

Hydrogen peroxide is the only oxidizing agent that has been found which will produce the compounds of the invention. The optimum quantity of hydrogen peroxide is two moles per mole of dithiocarbamate. The reaction is believed to take place in accordance with the following equation:

Nag JII-CH2CHz-I l-l )gNa 2H2O1 The oxidized nabam or equivalent soluble salt of another metal is then treated with a soluble salt of one of the divalent metals, zinc, manganese, cadmium or copper to precipitate the desired product which is removed by filtration.

The use of less than two moles of hydrogen peroxide results in a mixture of the metal salt of the unoxidized ethylene bisdithiocarbamate and the metal salt of oxidized alkylene bisdithiocarbamate. The use of more than two moles of peroxide results in the formation of some water-insoluble thiuram monoand disulfides which do not form metal salts.

The important feature of the process of the invention in addition to the use of hydrogen peroxide as the oxidizing agent is avoiding the addition of acid during the oxidation step. If the stoichiometric amount of acid is present to convert all of the original soluble salt to the dithiocarbamic acid, the product will of course be substantially all the thiuram monoand disulfides described above. However, by reducing substantially the amount of acid incorporated during the oxidation step, the oxygen becomes associated with the sulfur atoms of the dithiocarbamic acid, so that when the oxidized material is subsequently treated with a divalent metal, the desired compound containing both the divalent metal and the combined oxygen is obtained. Preferably no acid is added during the oxidation step. However, if an amount of acid between the stoichiometric amount and zero is added, the product will be a mixture of the thiuram monoand disulfides and the desired product substantially in the proportions determined by the amount of acid added.

The temperature of the reaction should be maintained as low as practical, that is below about 40 C., preferably in the range of 0 to 10 C. This may be accomplished, for example, by ice-cooling to remove the heat generated by the exothermic reaction. The reaction is carried out with stirring over a time interval of about 30 minutes, followed by stirring an additional 0.5 to 2 hours at about 10 to 15 C. to complete the reaction. A light precipitate of free sulfur may form which can be removed by filtration.

A water-soluble salt of the desired divalent metal is then added to precipitate the insoluble salt of oxidized alkylene bisdithiocarbamic acid as a slurry. This precipitate is filtered, washed with water and dried in a low temperature oven.

In avoiding the formation of thiuram rmonoand disulfides and providing the high yield of the oxygen-containing metal alkylene bisdithiocarbamates, it is important to coordinate the time of reaction, the temperature and the degree of agitation. A short time of reaction at low temperature and greater intensity of agitation generally works toward the production of the highest yields of the desired product. If temperatures toward the higher end of the range are maintained, then the time permitted for the reaction should be shorter. However, if temperatures toward the lower end of the range are maintained, then a longer time of reaction is desirable.

As a starting material for the reaction any soluble metal salt of an alkylene bisdithiocarbamic acid may be used such as sodium, potassium or calcium. They correspond to the structural formula:

SH RHS ll llll [-SCI GH CHNC-S]Z; in which Z is a metal and x is twice the reciprocal of the valence of the metal (e.g., 2 in the case of sodium and 1 for calcium), and R is H or CH The novel compounds of the invention are identified not only by the fact that they contain oxygen and one of the divalent metals as indicated above, but also by their infrared absorption spectra. The value of the infrared spectrum as a fingerprint identifying a chemical compound is well known and accepted. The technique is also useful in determining whether chemical manipulation of a compound with a known spectrum changes that C0111- pound in such a way as to eliminate some of its characteristic groupings of atoms and linkages and to introduce others with consequent changes in the infrared spectrum. Even if a new compound cannot be completely isolated or purified because of insolubility or because of inherent lability, its infrared spectrum will provide clues to its chemical identity.

Infrared spectra of the novel compositions of the invention, and those of related unoxidized alkylene bisdithiocarbarnates and their oxidation products from the prior art were determined by the potassium bromide disc technique, unless otherwise indicated, in a Perkin-Elmer double beam spectrophotometer, and are presented in FIGURES 1 through 9.

FIGURE 1 is an infrared absorption spectrum of the zinc salt of oxidized ethylene bisdithiocarbamic acid as determined both by the potassium bromide disc technique, and by the Nujol mull technique (which resolves the 8.2 1 absorption band);

FIGURE 2 shows the infrared spectrum of the zinc salt of partially oxidized nabam, that is the product formed when less than the stoichiometric two moles of hydrogen peroxide are used per mole of nabam;

FIGURE 3 shows the spectrum for zineb which is the zinc ethylene bisdithiocarbamate;

FIGURE 4 shows the infrared absorption spectrum for the manganous salt of oxidized nabam;

FIGURE 5 gives the infrared absorption spectrum for the trnanganous salt of partially oxidized nabam;

FIGURE 6 shows the infrared absorption spectrum for maneb which is the manganous ethylene bisdithiocarba mate;

FIGURE 7 shows the infrared absorption spectrum for ethylene bisthiuram disulfide which is an oxidation product of the ethylene bisdithiocarbamates and is known in the prior art;

FIGURE 8 also gives the infrared absorption spectrum for ethylene bisthiuram monosulfide, an ethylene bisdithiocarbamate oxidation product known in the prior art; and

FIGURE 9 gives the infrared absorption spectrum for the zinc salt of oxidized isopropyleue bisdithiocarbamic acid.

In the drawings the abscissa represents the wavelength in linear fashion, expressed in microns, and the ordinate shows (to a logarithmic scale) the percent absorbance.

The novel compositions of the invention are shown by their infrared spectra to differ from both the corresponding metal salts of unoxidized alkylene bisdithiocarbamic acid and from the prior art oxidation products thereof. Comparison of the infrared absorption bands in FIG- URES 1, 4 and 9 with those of FIGURES 3, 6, 7 and 8 shows that a new band is present in the 5.8 1 region of the oxidized products of the invention. This band is considered to be due to the presence of the carbonyl group, C=O, in the -s-c-1 r- II group, resulting from sulfur-oxygen interchange. The same band appears in the infrared spectra of the copper and cadmium salts of oxidized ethylene bisdithiocarbamic acid. The products of the invention are also seen to lack many of the bands which appear to be characteristic of the thiuram monosulfide, as well as the 10.5-1046a band present in the thiuram disulfide and in unoxidized ethylene bisdithiocarbamates.

Various preparations of the composition of the invention may differ considerably in elementary analysis, apparent empirical formula, but they nevertheless still give basically the same infrared absorption spectra indicating that the different preparations indeed contain basically the same new chemical substance or substances. We believe that the structure of the product formed by our process may have an open chain or polymeric form of structure which may contain recurring units as shown below:

SI-I RES where 1z=1 or more (the structure being cyclic when n is 1),

and

X is the divalent metal.

Our best analytical data indicate that the major portion of our product is a material described by the above empirical formula with possibly about of the material having a formula which could be written as follows:

where R, n and X have the values assigned above.

We believe that the compound shown in Formula 2 would be a natural decomposition product of the compound of Formula 1.

Typical preparations of the novel compositions follow.

Example 1.--Zinc salt of oxidized ethylene bisdithiocarba-mic acid To a cooled solution of sodium ethylene bisdithiocarbamate (116.4 g. of 22% active material, or 0.1 mole) was added hydrogen peroxide (13.6 g. of 50% active or 0.2 mole) in 100 ml. water dropwise over a period of minutes while maintaining the temperature of the reaction mixture below 0., preferably at 10-20 C. After standing for two hours, the mixture was filtered to remove a small quantity of pale yellow solid which precipitated during the peroxide addition. To the filtrate was added, with stirring, ml. of 1 M zinc sulfate solution (0.1 mole). The pH of the aqueous solution of nabam before oxidation was 10.5; after oxidation it was 9.511.0; after the addition of the zinc sulfate solution the pH dropped to 5-7. The resulting yellow slurry was stirred for one hour, filtered, and the precipitate washed with water, then dried in an oven at 60 C. The solid melted at -230 C. with decomposition. Analysis.-C, 16.41%, H, 2.20%; N, 9.12%; S, 35.94%; Zn 20.85%; 0, 12.0%. Infrared absorption bands occur at 5.8, 6.3, 6.75, 7.6, 8.2, 9.1, 10.1 and 11.8,u as shown in FIGURE 1.

Example 2.-Zinc salt of oxidized 1,2-propylene bisdithiocarbamic acid To sodium 1,2-propylene bisdithiocarbamate (the propylene group is the methyl ethylene group) (220 ml. of 24.5% active solution, 0.2 mole) in 200 ml. water was added dropwise with stirring and cooling hydrogen peroxide (27.2 g. of 50% active material, 0.4 mole) in 100 ml. water. The temperature of the reaction mixture was maintained at 5 C. over the 30-minute period of peroxide addition. The clear, orange-colored reaction solution was stirred for an additional 30 minutes at C. At the end of this time, the solution was still clear. To this oxidized dithiocarbamate solution was then added 200 ml. of 1 'M zinc sulfate solution (0.2 mole) with stirring. The resulting yellow slurry was stirred for one hour, filtered, washed, anddried at 50 C., yielding 58 grams of a solid melting at ISO-200 C. The infrared absorption spectrum of the product is presented in FIGURE 9. It is similar to that of the zinc salt of oxidized ethylene bisdithiocarbamic acid prepared according to Example 1 except that with the propylene compound there are additional absorption bands at 6.9, 7.25, 7.6, 9.5, and 9.8,u.

To sodium ethylene bisdithiocarbamate (2328 g. of 22% solution, 2 moles) cooled by the addition of 4000 g. of chopped ice was added hydrogen peroxide (272 g. of 50% active, 4 moles) in 800 ml. water. The peroxide was added dropwise with stirring over a period of 60 minutes while maintaining the reaction temperature at 1015 C. As soon as the addition was completed, cadmium nitrate (617 g. of Cd(NO -4H O in 1000 ml. water, 2 moles) was added to the oxidized sodium salt. The resulting pale yellow slurry was stirred for one hour, filtered, washed with water, and dried in the oven at 50 C. A yield of 708 g. of yellow solid melting at ISO-230 C. (with decomposition) was obtained. The infrared absorption spectrum determined on a Nujol mull of this product showed absorption bands at 5.8, 6.3, 6.6, 6.8 (Nujol), 7.3 (Nujol), 7.5, 8.2, 9.1, 10.1, 10.3, 10.9, and 11.6,u.

Example 4.Manganese salt of oxidized ethylene bisdithiocarbamic acid The procedure of Example 1 was followed, using 56 g. (0.05 mole) of sodium ethylene bisdithiocarbamate in 400 ml. water, oxidizing it with 6.8 g. of 50% active hydrogen peroxide (0.1 mole) in 80 ml. water at 10 C. over a period of one hour. To this solution was added manganese sulfate (50 ml. of 1 M solution, 0.05 mole), to obtain 8.6 g. of a light brown product which melted (with decomposition) at 250 C. Yield, 58% of theoretical. The infrared spectrum of this material determined on a potassium bromide disc had absorption bands at 5.9, 6.3, 6.9, 7.25, 7.6, 8.6, 10.1 and 11.8,u, as shown in FIGURE 4.

Example 5.-Copper salt of oxidized ethylene bisdithiocarbamic acid 6 and melting at 160190 C. was obtained. The infrared spectrum as determined on a Nujol mull of the product had absorption bands at 5.8, 6.3, 6.65, 6.8 (Nujol), 7.35 (Nujol), 8.1, 8.4, 9.6, 10.05, 10.6 and 1 1.7

It is to be noted that the infrared study of these five salts of oxidized alkylene bisdithiocarbamic acids showed no evidence of the presence of thiuram monoor disulfides, which materials are known to be formed by oxidation of alkylene bisdithiocarbamates under different conditions.

Example 6.Zinc I salt of, oxidized ethylene bisdithiocarbamic acid 25%, with zinc. sa'ltof unoxidized ethylene bisdithiocarbamic acid (zineb) The zinc salt of a mixture containing 25% of oxidized ethylene bisdithiocarbamic acid and 75 of unoxidized ethylene bisdithiocarbamic acid was prepared by the procedure of Example 1, using 2 moles of sodium ethylene bisdithiocarbamate (2329 g. of 22% active) and 68 g. (1 mole) of hydrogen peroxide 50% active in 200 ml. water, just sufiicient to oxidize 25% of the dithiocarbamate present. To the resulting clear, orange-colored solution was added zinc sulfate (323 g. or 2 moles ZnSO -H O in 1 liter water) with stirring. The resulting slurry was stirred for one hour, filtered, and the filter cake washed with water and dried in a vacuum oven at 55 C. Yield, 537 g. of white solid, M.P. ZOO-220 C. (with decomposition). The infrared spectrum of the product, illustrated in FIGURE 2, shows absorption characteristics of the zinc salts of both the oxidized and the unoxidized ethylene bisdithiocarbamic acids.

Example 7 .Manganese salt of oxidized ethylene bisdithiocarbamic acid 25%, with manganese salt of unoxidized ethylene bisdithiocarbamic acid (maneb) 75 characteristics of the manganese salts of both the oxidized and the unoxidized ethylene bisdithiocarbamic acids.

Example 8 aureus, and Salmonella typhosa, were conducted by plac-' ing discs dipped in various concentrations of the test compounds on agar plates seeded with one of the test organisms, then incubating the plates for 24 hours at F. The lowest concentration of the test chemical producing a clear zone denoting absence of bacterial growth around the discs was recorded in p.p.m.

TABLE I.-MICROBIOLOGICAL SCREENING TESTS Lowest concentration inhibiting growth, p.p.m.

Alkylene bisdithiocarbamate Color A. niger B. subtilis S. anreus S. typhosa Zine oxidizedethylene Yellow l 00 50 50 2050 Manganous oxidized-ethylene 'Ian 100 100 300 100 Cadmium oxidized-ethylene. Yellow. +1, 000 50 300 300 Cupric oxidized-ethylene.. Brown. +1, 000 300 300 300 Zinc oxidized-propylene Yellow 100 50 50 50 Key: means more than.

7 Example 9 Field trails of the compounds of the invention were carried out on growing potatoes in Florida. The fungicides were prepared in the form of wettable powders in 8 fides, and sulfuric acid (4.9 g. concentrated acid, 0.05 mole). The addition was made over a 30-minute period, and a white precipitate formed. After stirring for 15 minutes longer, the reaction mixture was cooled to C. and

the following formulation: 5 a further quantity of hydrogen peroxide (6.8 g.) in 20 ml. Parts by Weight Water was added over a 15-minute period to oxidize the Experimental fungi id 65 r maining dithiocarbamate to the oxygen-containing prod- McN-amee clay 1 27 ot of the invention. The yellow slurry which formed was Sfl 112 5 stirred for 15 minutes longer at 10-15 C., then zinc sul- Dal-van No 13 2 1O fate solution (50 ml. of l M solution, 0.05 mole) was Ultrawet K 4 1 add d rapidly. The slurry changed to a pale yellow color.

The final pH of the mixture was 6.5. The reaction mix- 100 ture was stirred for an additional 30 minutes at room temperature and then filtered. After washin three times 1 fl ll R.T.Vdbil a S: EEn ed lglr atghi r cipitated t z ali ium li t e df l i arwick 15 Water and drymg at m a forced draft Oven,

o gmeriz gd t ndiuht alkylnaphthalene sulfonate dispersant yield of 22 grams was olflamed M'P' 130-190 The of R. T. Vanderbilt Company, Inc. infrared spectrum of a Ntnol mull of the product showed Rgiilliglcgenzene sodium sulfonate dispersant of Atlantic bands at 5,8, 6.3, 6.6 (Nujol), 7.25 (Nujol), 7.5, 7 .85,

The experimental fungicides were mixed with water 0 8.2, 9.0, 9.45, 10.05, 10.45 and ll.75,u, indicating the presat the rate of 2 pounds Per 100 gallons and were applied ence of the zinc salt of oxidized ethylene b1sdithiocarat the rate of 125 gallons or 225 gauons per acre of bamic acid, thiuram sulfides, and a trace of the zinc salt growing Potatoes A11 Plots were Sprayed at the Same of unoxidizcd ethylene bisdithiocarbamic acid (zineb). rate on a given date Spraying was done on March 5 Biological screening of this mixed product shows the 12, 18, 22 d 28 d A il 3 10, 16 23 d 3() Percent 25 following minimum concentrations, in parts per million, defoliation of the plants by blight was determined on to be effective against these test olganismsi Aspergl'lllls April 12, 22 and 29 and on May 7 and 1 0, Th i ld niger 300, Bacillus subtilis 100, Staphylococcus aureus of potatoes at harvest on May 13 was determined and is 100, and Salmmlella lp trace at In a ppl g reported in the table below in pounds. One experimental t, carried out in accordance with the procedure deplot was left untreated as a, control, scribed in US. Patent NO. 2,977,316, diameters of the TABLE H.-POTATO FIELD TRIALS Average percent defoliation Yield, Ethylene bisdithlocarbamate I 1b..

None (untreated control).. 10 25 40 1 77. 5 3 87. 5 I 156 Zinc, oxidized 2 7.5 22.5 57.5 80 177 Manganese, oxidized 3 3 22. 5 55 75 7 209 Cupric, oxidized. 10 15 35 55 72.5 171 Cadmium, oxidized 1o 15 27.5 47.5 67.5 152 1 Highly significant, two standard deviations.

I Significant, one standard deviation;

Considerable weight is usually given to the May 7 zones of inhibition around plugs of soap in which the reading of defoliation. The May 10 reading determines material was incorporated at 1% concentration were 20, the persistence of the fungicide. Thus, each of the com- 17, and 20 mm. respectively, for the test bacteria B. subpounds of the invention has been shown to be an effectilis, S. aureus and S. typhosa. tive agricultural fungicide specifically for combatting fungus on potato plants. Example 12.-Manganous salt of oxidized ethylene bisdithiocarbamic acid, with thiuram sulfides Example 10 7 Potato field trials were carried out on the efiicacy of The procedure described in Example 11 s repeated the completely and the partially oxidized zinc and man- *P that Soluble mangaH01l$a1t Used lnstoad 0f ganese compounds in controlling early blight of potatoes. the Soluble Zlnc Salt, thereby forming 0f 'ihlllf The field trials were carried .out in the manner described l f and fifanganous Salt of X1d1Zed ethY1en and using formulations similar to those described in Exdlthiocarbamlc acid. The final slurry of solids was sepaample 9'. rated and purified and found to be a mixture of ethylene TABLE IIL-POTATO FIELD TRIALS Average percent defoliation Yield, Ethylene blsdithiocarbamate 1 None (untreated control)..." 10 25 40 77.5 87.5 156 Zinc,100% oxidized 2 7.5 22.5 57.5 80 177 5 2 s 20 47.5 so 178 Manganese, 100% oxidized 3 3 22. 5 75 209 Manganese, 25% oxidized (Example 7) 5 5 15 30 47. 5 196 These data show that the oxidized and the partlythiuram monosulfide, ethylene thiuram disulfide, the manoxidized ethylene bisdithiocarbamates are effective against ,gaIlOllS Salt of Oxidized ethylene blsdithiofial'bamic acid early blight of potatoes. and a small amount of maneb.

. By using an amount of peroxide in excess of the amount Example ir l fi l g blsdlthlo' needed for complete conversion to the oxidized alkylene car arms ac! W1 Imam es bisdithiocarbamate, and/or by adding some acid during To the sodium salt of ethylene bisdithiocarbamic acid the oxidation step, the relative proportions of metal salt (116.4 g. of 22% active material, 0.1 mole) in 100 ml. of oxidized nabam' and ethylene bisthiuram sulfides may water was added at 25 C., with cooling, hydrogen per be varied. Such' mixtures may contain from 20-80% ethoxide (6.8 g. of 50% active, 0.1 mole), sufficient to ylene bisthiuram sulfides and 80-20% metal salt of oxioxidize half the dithiocarbamate present to thiuram suldized alkylene bisdithiocarbamate. Because of the active properties as fungicides of the ethylene bisthiuram sulfides, such mixtures also have useful properties.

We claim:

1. The process which comprises oxidizing a soluble alkylene bisdithiocarbamate of the structure SH RHS where Z is a metal, x is twice the reciprocal of the valence of the metal, and R is a member of the group consisting of hydrogen and CH in solution with hydrogen peroxide without adding acid in amount to convert all of the bisdithiocarbamate to the corresponding bisdithiocarbamic acid, under conditions to produce a soluble oxygen-containing product, and controlling the amount of hydrogen peroxide used and limiting the amount of any acid added, to form said soluble product containing at least 5% oxygen, and thereafter adding to the solution a soluble salt of a divalent metal of the group consisting of zinc, manganese, copper and cadmium, thereby to precipitate a product containing oxygen and said divalent metal.

2. The process which comprises oxidizing a soluble alkylene bisdithiocarbamate of the structure SH RHS where Z is a metal, x is twice the reciprocal of the valence of the metal, and R is a member of the group consisting of hydrogen and CH in solution with hydrogen peroxide without adding acid in amount to convert all of the bisdithiocarbamate to the corresponding bisdithiocarbamic acid, under conditions to produce a soluble oxygen-containing product, and controlling the amount of hydrogen peroxide used and limiting the amount of any acid added, to form said soluble product containing at least 5% oxygen.

3. The process of claim 1 in which the dithiocarbamate has the structure shown in which R is hydrogen.

4. The process of claim 1 in which no acid is added during the process thereby to avoid the formation of substantial amounts of thiuram sulfides.

5. The process of claim 1 in which the amount of hydrogen peroxide used is about 2 moles per mole of alkylene bisdithiocarbamate.

6. The process of claim 1 in which the reactions are carried out in an aqueous solvent medium.

7. The process of claim 1 in which the temperature of the reaction medium during the oxidation reaction is maintained below about 40 C.

8. The process of claim 6 in which the temperature of the reaction medium during the oxidation reaction is maintained in the approximate range of 0-10 C. with agitation.

9. The process of claim 1 in which the dithiocarbamate has the structure shown in which R is hydrogen, and the divalent metal is zinc.

10. The process of claim 1 in which the dithiocar'oamate has the structure shown in which R is CH and the divalent metal is zinc.

11. The process of claim 1 in which the dithiocarbamate has the structure shown in which R is hydrogen, and the divalent metal is manganese.

12. The process of claim 1 in which the dithiocarbamate has the structure shown in which R is hydrogen, and the divalent metal is copper.

13. The process of claim 1 in which the dithiocarbamate has the structure shown in which R is hydro-gen, and the divalent metal is cadmium.

14. An oxygen-containing salt of an ethylene bisdithiocarbamic acid and a divalent metal selected from the group consisting of zinc, manganese, copper and cadmium, containing at least 5% of oxygen, and having substantially the infrared absorption spectrum shown in FIG- URE 1, with absorption bands at 5.8, 6.3, 6.75, 7.6, 8.2, 10.1 and ll.8,u..

15. The compound described in claim 14 in which the divalent metal is zinc and having an infrared absorption spectrum characterized by bands at 5.8, 6.3, 6.75, 7.6, 8.2, 9.1, 10.1 and 11.841.

16. The compound described in claim 14 in which the divalent metal is manganese and having an infrared absorption spectrum characterized by bands at 5.9, 6.3, 6.9, 7.25, 7.6, 8.6, 10.1 and 11.8,LL.

17. An oxygen-containing salt of propylene bisdithiocarbamic acid and a divalent metal selected from the group consisting of zinc, manganese, copper and cadmium, containing at least 5% oxygen, and having substantially the infrared absorption spectrum illustrated in FIGURE 9, with absorption bands at 5.8, 6.3, 6.7, 6.9, 7.25, 7.6, 8.4, 9.1, 9.5, 9.8, 10.2 and 11.8 11.

18. The compound described in claim 17 in which the divalent metal is zinc.

19. The compound described in claim 14 in which the divalent metal is copper and having an infrared absorption spectrum characterized by bands at 5.8, 6.3, 6.65, 8.1, 8.4, 9.6, 1 0.05, 10.6 and 11.7 1.

20. The compound described in claim 14 in which the divalent metal is cadmium and having an infrared absorption spectrum characterized by bands at 5.8, 6.3, 6.6, 7.5, 8.2, 9.1, 10.1, 10.3, 10.9 and 11.6

References Cited UNITED STATES PATENTS 1,453,515 5/1923 Murrill 260429 2,766,274 10/1956 Flenner 260-500 2,859,246 11/1958 Martin et al. 260-567 2,929,846 3/1960 Gates et al. 260-567 3,318,763 5/1967 Brooks et al l6722 3,322,802 5/1967 Brooks et al 260-429 FOREIGN PATENTS 234,970 6/1959 Australia.

HELEN M. MCCARTHY, Primary Examiner. A. P. DEMERS, Assistant Examiner. 

